稀土/碱土-锑金属氧卤簇基化合物的构筑及其质子传导性能研究

High-nuclearity cluster-based compounds present excellent physical and chemical properties that are different from that of the inorganic bulk materials or mononuclear compounds. This project will focus on construction of novel heterometallic oxohalide clusters integrating lanthanide (or alkaline-earth) metal ions and antimony (III), taking advantage of the synergistic structural tailoring effect of lone pair electrons of Sb(III) and terminal halogen ions, and the special coordination nature of lanthanide (or alkaline-earth) metal ions. The designed high-nuclearity oxohalide clusters will be used as secondary building units for the assembly of cluster-based compounds with structural diversity and benign proton-conducting properties, with the aid of functional organic ligands, metallic complexes or inorganic groups as linkers. It is proposed that the ways of decoration on the surface of cluster, modulation for the cavity, incorporation of sulfonic groups and imidazole groups will improve the proton-conducting property. We have successfully prepared Pr/Ba-Sb(III) oxochloride nanocluster with high-nuclearity, also a series of Pr-Sb(III) oxochloride cluster-based hybrids with tunable structures by modulating organic ligands, and the proton-conductivity can reach the order of 10-2, which provide a thorough grounding for the project.

高核簇基结构化合物往往呈现有别于无机块体材料和单核化合物的优异物化性质。本项目致力于一类新型金属氧卤簇基结构的设计合成及其质子传导性能研究。提出“利用锑(III)的孤电子对和端基配位卤素离子对结构的协同剪裁作用，及稀土/碱土金属离子的亲氧、亲卤性和高配位数特点，构筑稀土/碱土-锑金属高核氧卤簇”的独特策略，解决高核氧卤簇的构筑难题；拟以高核氧卤簇为次级构建单元，通过选择功能性有机配体、金属络合物或无机基团作为连接体，实现结构多样、稳定性高的簇基结构的组装；应用修饰簇表面、调控结构孔隙、引入磺酸基团和咪唑阳离子等手段提升化合物的高温非水质子传导性能，明晰传导机制，开发出稳定性高、性能优良的新型质子传导材料。前期工作已获得了Pr-Sb(III)和Ba-Sb(III)两个系列的高核氧氯纳米簇及其簇基结构，并发现Ba-Sb(III)基化合物质子传导率达10-2量级，为项目目标的实现奠定了坚实基础。

针对高核簇基功能材料设计合成的难题，开展了稀土/碱土/过渡-锑金属高核氧卤簇基质子传导功能材料研究。从结构和性能角度出发，开发新型高核簇基功能材料的构筑策略。利用结构剪裁策略构筑了一例具有新颖{Ba@Ba12@Sb36}多层核壳结构的高核氧氯化物簇，该高核簇可组装成三维框架或二维层状结构。这两例化合物具有湿度和温度依赖的质子传导性能，其质子传导率可与性能优越的MOFs、多酸等材料的结果相媲美（Chem. Comm. 2019, 55, 7442-7445）。首次合成了两例同时含有第一和第二过渡金属的Sb氧簇，两个化合物均呈现较好的质子传导性能（Dalton Trans. 2020, DOI: 10.1039/C9DT04333K）。研究对于设计新颖高核簇基结构具有借鉴意义，在制备高传导率的簇基质子传导材料方面具有潜在的应用价值，对于开发燃料电池新能源材料具有现实意义。.在项目执行期间，共发表SCI论文8篇，其中一区论文Angew. Chem. Int. Ed.和Chem. Comm.各1篇，二区论文5篇；发表会议论文2篇。协助培养博士后出站1名、博士毕业生1名，协助指导在读博士研究生1名。圆满完成了项目计划书中的各项任务。